A Selenourea-Thiourea Brønsted Acid Catalyst Facilitates Asymmetric Conjugate Additions of Amines to α,β-Unsaturated Esters
β-Amino esters are obtained with high levels of enantioselectivity via the conjugate addition of cyclic amines to unactivated α,β-unsaturated esters. A related strategy enables the kinetic resolution of racemic cyclic 2-arylamines, using benzyl acrylate as the resolving agent. Reactions are facilita...
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| Veröffentlicht in: | Journal of the American Chemical Society 2020-03, Vol.142 (12), p.5627-5635 |
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| container_title | Journal of the American Chemical Society |
| container_volume | 142 |
| creator | Lin, Yingfu Hirschi, William J Kunadia, Anuj Paul, Anirudra Ghiviriga, Ion Abboud, Khalil A Karugu, Rachael W Vetticatt, Mathew J Hirschi, Jennifer S Seidel, Daniel |
| description | β-Amino esters are obtained with high levels of enantioselectivity via the conjugate addition of cyclic amines to unactivated α,β-unsaturated esters. A related strategy enables the kinetic resolution of racemic cyclic 2-arylamines, using benzyl acrylate as the resolving agent. Reactions are facilitated by an unprecedented selenourea-thiourea organocatalyst. As elucidated by DFT calculations and 13C kinetic isotope effect studies, the rate-limiting and enantiodetermining step of the reaction is the protonation of a zwitterionic intermediate by the catalyst. This represents a rare case in which a thiourea compound functions as an asymmetric Brønsted acid catalyst. |
| doi_str_mv | 10.1021/jacs.9b12457 |
| format | Article |
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Am. Chem. Soc</addtitle><description>β-Amino esters are obtained with high levels of enantioselectivity via the conjugate addition of cyclic amines to unactivated α,β-unsaturated esters. A related strategy enables the kinetic resolution of racemic cyclic 2-arylamines, using benzyl acrylate as the resolving agent. Reactions are facilitated by an unprecedented selenourea-thiourea organocatalyst. As elucidated by DFT calculations and 13C kinetic isotope effect studies, the rate-limiting and enantiodetermining step of the reaction is the protonation of a zwitterionic intermediate by the catalyst. 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Am. Chem. Soc</addtitle><date>2020-03-25</date><risdate>2020</risdate><volume>142</volume><issue>12</issue><spage>5627</spage><epage>5635</epage><pages>5627-5635</pages><issn>0002-7863</issn><issn>1520-5126</issn><eissn>1520-5126</eissn><abstract>β-Amino esters are obtained with high levels of enantioselectivity via the conjugate addition of cyclic amines to unactivated α,β-unsaturated esters. A related strategy enables the kinetic resolution of racemic cyclic 2-arylamines, using benzyl acrylate as the resolving agent. Reactions are facilitated by an unprecedented selenourea-thiourea organocatalyst. As elucidated by DFT calculations and 13C kinetic isotope effect studies, the rate-limiting and enantiodetermining step of the reaction is the protonation of a zwitterionic intermediate by the catalyst. 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| source | ACS Publications; MEDLINE |
| subjects | Amines - chemical synthesis Amines - chemistry Catalysis Density Functional Theory Esters - chemical synthesis Esters - chemistry Kinetics Models, Chemical Organoselenium Compounds - chemistry Thiourea - chemistry Urea - analogs & derivatives Urea - chemistry |
| title | A Selenourea-Thiourea Brønsted Acid Catalyst Facilitates Asymmetric Conjugate Additions of Amines to α,β-Unsaturated Esters |
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